CN109309254A - Electrolyte and electrochemical energy storage device - Google Patents

Electrolyte and electrochemical energy storage device Download PDF

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CN109309254A
CN109309254A CN201710626357.4A CN201710626357A CN109309254A CN 109309254 A CN109309254 A CN 109309254A CN 201710626357 A CN201710626357 A CN 201710626357A CN 109309254 A CN109309254 A CN 109309254A
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electrolyte
unsubstituted
substituted
quaternary ammonium
content
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CN109309254B (en
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王小梅
姜彬
付成华
韩昌隆
刘继琼
周艳
朱建伟
刘文浩
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Contemporary Amperex Technology Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/58—Liquid electrolytes
    • H01G11/64—Liquid electrolytes characterised by additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/56—Solid electrolytes, e.g. gels; Additives therein
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Secondary Cells (AREA)

Abstract

The application provides an electrolyte and an electrochemical energy storage device. The electrolyte includes an electrolyte salt and an additive. The additive comprises sulfonate cyclic quaternary ammonium salt and fluoroether compound. The combined action of the positive electrode and the negative electrode can enable a layer of compact, uniform and stable passive film to be formed on the surfaces of the positive electrode and the negative electrode of the electrochemical energy storage device, especially a low-impedance and compact solid electrolyte interface film can be formed on the surface of the negative electrode, so that continuous oxidation and reduction reactions between the electrolyte and the positive electrode and between the electrolyte and the negative electrode can be avoided, the interface impedance of the positive electrode and the negative electrode can be reduced, and the storage and gas generation of the electrochemical energy storage device in the use process can be reduced, so that the electrochemical energy storage device has better high-temperature storage performance.

Description

Electrolyte and electrochemical energy storage device
Technical field
This application involves energy storage device field more particularly to a kind of electrolyte and electrochemical energy storage device.
Background technique
As increasingly depleted and environmental pollution the pressure of fossil energy is increasing, there is an urgent need to a kind of new for automobile industry The type energy provides driving for it, and lithium ion battery is due to having the characteristics that energy density height, memory-less effect, operating voltage are high de- Grain husk and go out, making it currently becomes the preferred option of new-energy automobile electrical source of power.However as the expansion of electronics market demand Big and power, energy storage device development, requirement of the people to lithium ion battery are continuously improved, and exploitation has high-energy density and full The lithium ion battery of sufficient fast charging and discharging becomes the task of top priority.Currently, effective method be improve the voltage of electrode active material, Compacted density and the suitable electrolyte of selection.
Currently, widely applied electrolyte is usually using lithium hexafluoro phosphate as electrolytic salt and with ring in lithium ion battery Shape carbonic ester and the mixture of linear carbonate are the electrolyte of organic solvent, however above-mentioned electrolyte is there are many deficiencies, Specifically under high voltages, the high-temperature storage performance of lithium ion battery is poor, and lithium ion battery faces below in long-term circulation The problem of capacity rapid decay.Wherein, important component of the electrolyte as lithium ion battery, to the electricity of lithium ion battery Chemical property has great influence, and the composition by improving electrolyte can improve lithium ion battery in high pressure to a certain extent Under high-temperature storage performance.
Summary of the invention
In view of the problems in the background art, the application is designed to provide a kind of electrolyte and electrochemical energy storage dress It sets, the electrochemical energy storage device has preferable high-temperature storage performance.
In order to achieve the above object, in the one side of the application, this application provides a kind of electrolyte comprising electrolyte Salt and additive.The additive includes sulphonic acid ester cyclic quaternary ammonium salts and fluorine ether compound.
In the another aspect of the application, this application provides a kind of electrochemical energy storage devices comprising the application is on the one hand Electrolyte.
Compared with the existing technology, the application has the beneficial effect that
The electrolysis additive of the application includes sulphonic acid ester cyclic quaternary ammonium salts and fluorine ether compound, electrochemistry can be made to store up The positive and negative electrode surface of energy device is respectively formed one layer of densification, uniform and stable passivating film, is especially capable of forming in negative terminal surface Low ESR and the solid electrolyte interface film of densification, can be to avoid occurring lasting oxidation and also between electrolyte and positive and negative electrode Original reaction, reduces the interface impedance of positive and negative electrode, while can also reduce the storage of electrochemical energy storage device in use and produce Gas makes electrochemical energy storage device have preferable high-temperature storage performance.
Specific embodiment
The following detailed description of the electrolyte and electrochemical energy storage device according to the application.
Illustrate the electrolyte according to the application first aspect first.
Electrolyte according to the application first aspect includes electrolytic salt and additive.The additive includes sulphonic acid ester Cyclic quaternary ammonium salts and fluorine ether compound.
In the electrolyte according to the application first aspect, the sulphonic acid ester cyclic quaternary ammonium salts and fluorine ether compound The positive and negative electrode surface of electrochemical energy storage device can be made to be respectively formed one layer of densification, uniform and stable passivating film, especially negative Pole surface is capable of forming the solid electrolyte interface film (SEI film) of Low ESR and densification, reduces connecing for positive and negative electrode and electrolyte Touching, so as to avoid electrolyte that lasting oxidation reaction and reduction reaction occur on positive and negative electrode surface, and then reduces electrolysis The decomposition of liquid, avoids internal resistance from rising, while can also reduce the storage of electrochemical energy storage device in use and produce gas, makes electricity Chemical energy storage device has preferable high-temperature storage performance.The reason is that the reduction potential of sulphonic acid ester cyclic quaternary ammonium salts exists 1.5V or so, when voltage reaches 1.5V, sulphonic acid ester cyclic quaternary ammonium salts are orientable to be migrated to cathode, and preferentially forms one in cathode Layer it is fine and close, lead the ionic good solid electrolyte interface film being made of alkyl sulfonic acid metal salt, so as to prevent electrolyte With negative reaction, the high-temperature storage performance of electrochemical energy storage device is improved.And fluorine ether compound can then form a film in anode, together When due to the oxidizing potential of fluorine ether compound it is higher, thus can reduce electrochemical energy storage device storage produce gas, thus into one Step improves the high-temperature storage performance of electrochemical energy storage device, but the content of fluorine ether compound is too high will lead to electrochemical energy storage device Dynamic performance be deteriorated.Therefore, under the collective effect of sulphonic acid ester cyclic quaternary ammonium salts and fluorine ether compound, electrochemical energy storage dress It sets with preferable high-temperature storage performance.
In the electrolyte according to the application first aspect, the electrolyte is liquid electrolyte, solid polymer Electrolyte or gel polymer electrolytes.Due to liquid electrolyte and solid polymer electrolyte, gel polymer electrolytes The mechanism of action is similar, therefore is only illustrated in this application with liquid electrolyte citing.
In the electrolyte according to the application first aspect, the sulphonic acid ester cyclic quaternary ammonium salts are selected from shown in formula 1 One or more of compound；In formula 1, R11Alkyl selected from-CN, substituted or unsubstituted C1~12 replaces or does not take The alkenyl of C2~12 in generation, the alkynyl of substituted or unsubstituted C2~12, the alkoxy of substituted or unsubstituted C1~12, substitution Or one of acyloxy of unsubstituted C1~12；R12Alkylidene selected from substituted or unsubstituted C1~12 replaces or not The alkenylene of substituted C2~12, the alkynylene of substituted or unsubstituted C2~12, substituted or unsubstituted C1~12 alkylene One of acyl group；R13The alkenyl of alkyl, substituted or unsubstituted C2~12 selected from substituted or unsubstituted C1~12 replaces Or the alkynyl of unsubstituted C2~12, the alkoxy of substituted or unsubstituted C1~12, substituted or unsubstituted C1~12 acyl One of oxygroup, the aryl of substituted or unsubstituted C6~22, heterocyclic base of substituted or unsubstituted C5~22；R14Selected from taking The alkylidene of generation or unsubstituted C1~3；Substituent group is selected from one or more of-CN, halogen atom.
In formula 1,Indicate anion,Selected from F-、NO3 -、SO4 2-、PF6 -、PF4 -、AsF6 -、
One of.
In the electrolyte according to the application first aspect, in formula 1, it is preferable that R11Selected from substituted or unsubstituted C1~6 alkyl or one of halogenated alkyl, R12One of alkylidene selected from substituted or unsubstituted C1~12, R13One of alkyl or halogenated alkyl selected from substituted or unsubstituted C1~6, R14Selected from substituted or unsubstituted C1~2 One of alkylidene.
In the electrolyte according to the application first aspect, the cation group of the sulphonic acid ester cyclic quaternary ammonium salts can It is selected from
One of.
In the electrolyte according to the application first aspect, specifically, the sulphonic acid ester cyclic quaternary ammonium salts be can be selected from One or more of following compounds:
Compound 1-1,Compound 1-2,Compound 1-3,Compound 1-4,Compound 1-5,
Compound 1-6.
In the electrolyte according to the application first aspect, the fluorine ether compound is from 2 compound represented of formula One or more；In formula 2, R21、R22It is each independently selected from the fluoro-alkyl of C1~10, the fluoroalkyl of C1~10 One of.
R21-O-R22Formula 2
In the electrolyte according to the application first aspect, specifically, the fluorine ether compound can be selected from followingization Close one or more of object；
Compound 2-1,
Compound 2-2,
Compound 2-3,
Compound 2-4.
In the electrolyte according to the application first aspect, the content of sulphonic acid ester cyclic quaternary ammonium salts is very few, formation Positive and negative anodes passivating film is not sufficient to that electrolyte is prevented further to react, also unobvious to the improvement of electrochemical energy storage device performance； And content is excessive, then the impedance on positive and negative anodes increases, and can deteriorate the performance of electrochemical energy storage device.Preferably, the sulfonic acid The content of ester cyclic quaternary ammonium salts is the 0.05%~10% of the electrolyte gross mass.It is further preferred that the sulphonic acid ester ring The content of shape quaternary ammonium salt is the 0.1%~5% of the electrolyte gross mass.
In the electrolyte according to the application first aspect, the content of fluorine ether compound is very few, to electrochemical energy storage The performance improvement of device is unobvious；And content is excessive, then since electrolysis fluid viscosity increases, can deteriorate the dynamic of electrochemical energy storage device Mechanical property.Preferably, the content of the fluorine ether compound is the 0.1%~8% of the electrolyte gross mass.Further preferably Ground, the content of the fluorine ether compound are the 1%~5% of the electrolyte gross mass.
In the electrolyte according to the application first aspect, the concentration of the electrolytic salt is not limited specifically, It can be selected according to actual needs.Specifically, the content of the electrolytic salt be the electrolyte gross mass 6%~ 25%.Preferably, the content of the electrolytic salt is the 6%~20% of the gross mass of the electrolyte.It is further preferred that institute State electrolytic salt content be the electrolyte gross mass 10%~15%.
In the electrolyte according to the application first aspect, the electrolytic salt in the electrolyte can be selected from lithium salts or Sodium salt.
In the electrolyte according to the application first aspect, the type of the lithium salts is not limited specifically, can root It is selected according to actual demand.Preferably, the lithium salts includes at least LiPF6.The lithium salts can further include LiBF4、 LiClO4、LiAsF6、LiSbF6、LiBOB、LiDFOB、LiN(SO2F)2、LiTFSI、LiPO2F2、LiTFOP、LiN(SO2RF)2、 LiN(SO2F)(SO2RF one or more of), wherein RF=CnF2n+1, indicate that saturation perfluoroalkyl, n are whole in 1~10 Number.
In the electrolyte according to the application first aspect, the type of the sodium salt is not limited specifically, can root It is selected according to actual demand.Specifically, the sodium salt can be selected from NaPF6、NaBF4、NaClO4、NaAsF6、NaCF3SO3、NaN (CF3SO2)2、NaN(C2F5SO2)2、NaN(FSO2)2One or more of.
In the electrolyte according to the application first aspect, the electrolyte further includes organic solvent, described organic The type of solvent can be selected according to actual needs there is no specific limitation.Preferably, using non-aqueous organic solvent.Institute State the carbonic ester and/or carboxylate that non-aqueous organic solvent may include any kind.The carbonic ester may include cyclic carbonate with And the mixture of linear carbonate.The non-aqueous organic solvent may also include the halogenated compound of carbonic ester.Specifically, described to have Solvent can be selected from ethylene carbonate, propylene carbonate, butylene carbonate, pentylene, fluoroethylene carbonate, carbonic acid two Methyl esters, diethyl carbonate, dipropyl carbonate, methyl ethyl carbonate, methyl formate, Ethyl formate, ethyl acetate, propyl propionate, third One or more of acetoacetic ester, gamma-butyrolacton, tetrahydrofuran.
Secondly illustrate the electrochemical energy storage device according to the application second aspect.
It include the electricity according to the application first aspect according to electrochemical energy storage device described in the application second aspect Solve liquid.
In the electrochemical energy storage device according to the application second aspect, the electrochemical energy storage device further includes just Pole piece, negative electrode tab, isolation film and pack case etc..
In the electrochemical energy storage device according to the application second aspect, it should be noted that the electrochemistry storage Energy device can be lithium ion battery, sodium-ion battery, Zinc ion battery or supercapacitor.In embodiments herein, only The embodiment that electrochemical energy storage device is lithium ion battery is shown, but the application is without being limited thereto.
In lithium ion battery, positive plate includes plus plate current-collecting body and the positive diaphragm that is set on plus plate current-collecting body.Institute Stating positive diaphragm includes positive electrode active materials, and the anode diaphragm may also include conductive agent, binder.Positive electrode active materials are optional From cobalt acid lithium (LiCoO2), lithium nickelate (LiNiO2), the LiMn2O4 (LiMn of spinel-type2O4), the LiMPO of olivine-type4, ternary Material LiaNixAyB(1-x-y)O2One or more of.Wherein, in the LiMPO of olivine-type4In, M is selected from Co, Ni, Fe, Mn, V One or more of；In ternary material LiaNixAyB(1-x-y)O2In, A, B are each independently selected from one of Co, Al, Mn, And A and B be not identical, 0.95≤a≤1.2,0 < x < 1,0 < y < 1, and x+y < 1.The not specific limit of the type of conductive agent and binder System, can be selected according to actual needs.
In lithium ion battery, negative electrode tab includes negative current collector and the cathode membrane that is set on negative current collector.Institute Stating cathode membrane includes negative electrode active material, and the cathode membrane may also include conductive agent, binder.Negative electrode active material is optional Comfortable voltage < 2V (vs.Li/Li+) when can be embedded in the material of lithium.Specifically, the negative electrode active material can be selected from natural stone The micro- carbon ball of ink, artificial graphite, interphase (referred to as MCMB), hard carbon, soft carbon, silicon, silico-carbo compound, Li-Sn alloy, Li- Sn-O alloy, Sn, SnO, SnO2, spinel structure lithiumation TiO2-Li4Ti5O12, one or more of Li-Al alloy.It leads The not specific limitation of the type of electric agent and binder, can be selected according to actual needs.The negative electrode tab also can be used directly Metal lithium sheet.
In lithium ion battery, the type of the isolation film is not specifically limited, and can be selected according to actual needs, tool Body, the isolation film can be selected from polyethylene film, polypropylene screen, polyvinylidene fluoride film and their multilayer complex films.
Below with reference to embodiment, the application is further described.It should be understood that these embodiments be merely to illustrate the application without For limiting scope of the present application.The case where electrochemical energy storage device is lithium ion battery, but this Shen are only shown in embodiment It please be without being limited thereto.
In the following embodiments, reagent, material and the instrument used such as not special explanation, it is commercially available to obtain , used sulphonic acid ester cyclic quaternary ammonium salts can refer to Chinese patent CN105845981A disclosed on August 10th, 2016.
Lithium ion battery in embodiment 1~12 and comparative example 1~7 is prepared by the following method:
(1) preparation of positive plate
By positive electrode active materials cobalt acid lithium (LiCoO2), conductive agent acetylene black, binder polyvinylidene fluoride in mass ratio 98:1:1 is mixed, and solvent N-methyl pyrilidone is added, and stirring is uniform to stable system under de-airing mixer effect, is obtained Obtain anode sizing agent；Anode sizing agent is evenly applied on the plus plate current-collecting body aluminium foil with a thickness of 12 μm；Aluminium foil is dried in room temperature After be transferred to 120 DEG C of oven drying 1h, then by cold pressing, cutting obtain positive plate.
(2) preparation of negative electrode tab
By negative electrode active material artificial graphite, thickener sodium carboxymethylcellulose (CMC), binder butadiene-styrene rubber according to matter Amount is mixed than 98:1:1, and deionized water is added, and obtains negative electrode slurry under de-airing mixer effect；Negative electrode slurry is uniform Coated on the negative current collector copper foil with a thickness of 8 μm；Copper foil is transferred to 120 DEG C of oven drying 1h after room temperature is dried, so Afterwards by being cold-pressed, cutting to obtain negative electrode tab.
(3) preparation of electrolyte
In water content < 10ppm argon atmosphere glove box, by ethylene carbonate (EC), methyl ethyl carbonate (EMC), carbon Diethyl phthalate (DEC) is that EC:EMC:DEC=1:1:1 is mixed according to volume ratio, then by sufficiently dry lithium salts LiPF6 It is dissolved in mixed organic solvents, sulphonic acid ester cyclic quaternary ammonium salts and fluorine ether compound is added later, obtain electricity after mixing Solve liquid.Wherein, LiPF6Content be electrolyte gross mass 12.5%.Used sulphonic acid ester cyclic quaternary in electrolyte The specific type and content of salt and fluorine ether compound are as shown in table 1, and in table 1, sulphonic acid ester cyclic quaternary ammonium salts and fluorine etherificate Close the mass percent that the content of object is calculated for the gross mass based on electrolyte.
(4) preparation of isolation film
Select the polypropylene isolation film of 16 μ m-thicks (model A273 is provided by Celgard company).
(5) preparation of lithium ion battery
Positive plate, isolation film, negative electrode tab are folded in order, isolation film is between positive and negative plate and plays isolation Effect, then winding obtains naked battery core；Naked battery core is placed in outer packing shell, the above-mentioned electrolyte prepared is injected into drying In naked battery core afterwards, by processes such as Vacuum Package, standing, chemical conversion, shapings, lithium ion battery is obtained.
The parameter of table 1 embodiment 1~12 and comparative example 1~7
The test process of lithium ion battery will be illustrated next.
(1) the high-temperature storage performance test of lithium ion secondary battery
At 25 DEG C, by lithium ion battery with 1C constant-current charge to 4.5V, then it is less than with 4.5V constant-voltage charge to electric current 0.05C tests the discharge capacity of lithium ion battery at this time and is denoted as D0 later with 0.5C constant-current discharge to 3.0V；Again with 1C perseverance Current charge is less than 0.05C later with 4.5V constant-voltage charge to electric current, then lithium ion battery is placed at 60 DEG C and is stored to 4.5V 30 days, after storing, with 1C constant-current discharge to 3.0V；Again with 1C constant-current charge to 4.5V, then with 4.5V constant-voltage charge It is less than 0.05C to electric current, later with 0.5C constant-current discharge to 3.0V, tests the discharge capacity of lithium ion battery at this time and be denoted as D1.15 lithium ion batteries of every group of test, are averaged.
Capacity retention ratio (%)=[D1/D0] × 100% of 60 DEG C of lithium ion battery storages 30 days.
(2) high temperature storage of lithium ion battery produces gas test
It with 0.5C constant-current charge to voltage is 4.5V by lithium ion battery, then extremely with 4.5V constant-voltage charge at 25 DEG C Electric current is 0.05C, tests the thickness of lithium ion battery at this time and is denoted as h0；Lithium ion battery is put into 60 DEG C of constant temperature later Case, storage are taken out after 180 days, are tested the thickness of lithium ion battery at this time and are denoted as h1.15 lithium ion secondary electricity of every group of test Pond is averaged.
Thickness swelling (%)=[(the h1-h0)/h0] × 100% of 60 DEG C of lithium ion battery storages 180 days.
The performance test results of table 2 embodiment 1~12 and comparative example 1~7
From the Correlative data analysis of table 2 it is found that lithium ion battery is in sulphonic acid ester cyclic quaternary ammonium salts and fluorine ether compound There can be preferable high-temperature storage performance under collective effect.
The analysis in comparative example 1~3 it is found that sulphonic acid ester cyclic quaternary ammonium salts and fluorine ether compound is not added in comparative example 1, The high temperature storage capacity retention ratio and high temperature storage thickness swelling of lithium ion battery are all poor；When only containing sulphur in electrolyte When acid esters cyclic quaternary ammonium salts (comparative example 2), the high temperature storage capacity retention ratio and high temperature storage thickness swelling of lithium ion battery It can be improved to a certain extent, but the improvement amplitude of wherein high temperature storage thickness swelling is relatively small, it is difficult to meet real Border use demand；When only containing fluorine ether compound (comparative example 3) in electrolyte, the high temperature storage capacity of lithium ion battery is kept Rate and high temperature storage thickness swelling can also be improved to a certain extent, but the wherein improvement of high temperature storage capacity retention ratio Amplitude is relatively small, is still difficult to meet the actual needs.
The analysis in embodiment 1~12 and comparative example 4~7 it is found that be added sulphonic acid ester cyclic quaternary ammonium salts simultaneously in electrolyte And fluorine ether compound, lithium ion battery high temperature storage capacity retention ratio with higher and lower high temperature storage thickness swelling Rate, while it is understood that the variation of the specific type and dosage of sulphonic acid ester cyclic quaternary ammonium salts and fluorine ether compound is inevitable straight The performance for influencing electrolyte is connect, to influence the improvement to performance of lithium ion battery.
In comparative example 4, the content of sulphonic acid ester cyclic quaternary ammonium salts is insufficient, keeps to the high temperature storage capacity of lithium ion battery The improvement of rate is weaker.In Examples 1 to 5, with the increase of sulphonic acid ester cyclic quaternary salt content, the height of lithium ion battery is gentle Storage capacity retention ratio and high temperature storage thickness swelling significantly improve.When the too high levels of sulphonic acid ester cyclic quaternary ammonium salts, Such as in comparative example 5, the high temperature storage capacity retention ratio of lithium ion battery can be deteriorated.
In comparative example 6, the content of fluorine ether compound is insufficient, to changing for the high temperature storage thickness swelling of lithium ion battery It is kind weaker.In embodiment 6~9 and embodiment 3, as fluorine ether compound content increases, stores and hold in high-temperature lithium ion battery In the case where conservation rate is measured without obvious degradating trend, the high temperature storage thickness swelling of lithium ion battery is significantly reduced.When fluorine ether When the too high levels of compound, such as in comparative example 7, since dynamic performance is deteriorated, it is degrading lithium ion battery instead High temperature storage capacity retention ratio.
Therefore the content of sulphonic acid ester cyclic quaternary ammonium salts and fluorine ether compound is too little or too much is unfavorable for improving on the whole The performance of lithium ion battery, but required in relatively low or more secondary use demand for some, it equally can be certain Improve the high-temperature storage performance of lithium ion battery in degree.
The announcement of book according to the above description, the application those skilled in the art can also carry out above embodiment Change and modification appropriate.Therefore, the application is not limited to specific embodiment disclosed and described above, to the application's Some modifications and changes should also be as falling into the protection scope of claims hereof.

Claims (10)

1. a kind of electrolyte, comprising:
Electrolytic salt；And
Additive；
It is characterized in that,
The additive includes sulphonic acid ester cyclic quaternary ammonium salts and fluorine ether compound.
2. electrolyte according to claim 1, which is characterized in that the sulphonic acid ester cyclic quaternary ammonium salts are selected from shown in formula 1 One or more of compound；
In formula 1, R11The alkenyl of alkyl, substituted or unsubstituted C2~12 selected from-CN, substituted or unsubstituted C1~12, The alkynyl of substituted or unsubstituted C2~12, the alkoxy of substituted or unsubstituted C1~12, substituted or unsubstituted C1~12 One of acyloxy；
R12The alkenylene of alkylidene, substituted or unsubstituted C2~12 selected from substituted or unsubstituted C1~12 replaces or not One of the alkynylene of substituted C2~12, alkylene acyl group of substituted or unsubstituted C1~12；
R13It is the alkenyl of alkyl, substituted or unsubstituted C2~12 selected from substituted or unsubstituted C1~12, substituted or unsubstituted The alkynyl of C2~12, the alkoxy of substituted or unsubstituted C1~12, substituted or unsubstituted C1~12 acyloxy, replace Or one of the aryl of unsubstituted C6~22, heterocyclic base of substituted or unsubstituted C5~22；
R14Alkylidene selected from substituted or unsubstituted C1~3；
Substituent group is selected from one or more of-CN, halogen atom；
Indicate anion,Selected from F-、NO3 -、SO4 2-、PF6 -、PF4 -、AsF6 -、(FSO2)2N-、
One of.
3. electrolyte according to claim 2, which is characterized in that the cation group of the sulphonic acid ester cyclic quaternary ammonium salts is selected from
One of.
4. electrolyte according to claim 3, which is characterized in that the sulphonic acid ester cyclic quaternary ammonium salts are selected from following compounds One or more of:
5. electrolyte according to claim 1, which is characterized in that the fluorine ether compound is selected from 2 compound represented of formula One or more of；
3R21-O-R22Formula 2
In formula 2, R21、R22It is each independently selected from one of the fluoro-alkyl of C1~10, fluoroalkyl of C1~10.
6. electrolyte according to claim 5, which is characterized in that the fluorine ether compound in following compounds one Kind is several；
7. electrolyte according to claim 1, which is characterized in that
The content of the sulphonic acid ester cyclic quaternary ammonium salts is the 0.05%~10% of the electrolyte gross mass, it is preferable that the sulphur The content of acid esters cyclic quaternary ammonium salts is the 0.1%~5% of the electrolyte gross mass；
The content of the fluorine ether compound is the 0.1%~8% of the electrolyte gross mass, it is preferable that the fluorine ether compound Content be the electrolyte gross mass 1%~5%.
8. electrolyte according to claim 1, which is characterized in that the content of the electrolytic salt is the total matter of the electrolyte The 6%~25% of amount, it is preferable that the content of the electrolytic salt is the 6%~20% of the electrolyte gross mass, further excellent Selection of land, the content of the electrolytic salt are the 10%~15% of the electrolyte total weight.
9. electrolyte according to claim 1, which is characterized in that the electrolyte is liquid electrolyte, solid polymer Electrolyte or gel polymer electrolytes.
10. a kind of electrochemical energy storage device, which is characterized in that including electrolyte according to claim 1 to 9.
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